Water dispersible or water soluble copolymer containing UV-absorbing monomer

ABSTRACT

The invention relates to novel water-dispersible or water-soluble copolymers which contain at least one UV-absorbing monomer and one hydrophilic monomer component. These copolymers may be used in fabric care compositions and provide anti-fading and soil release benefits.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The subject invention relates to novel water dispersible orwater-soluble copolymers which contain at least one UV-absorbing monomerand one hydrophilic monomer component. The copolymers may optionallycontain a hydrophobic monomer component (i.e., if you have awater-soluble UV absorber, then you need hydrophobic groups to ensure itadsorbs). These copolymers may be used in fabric care compositions andprovide anti-fading and soil release benefits. Because of their UVabsorbancy, such copolymer could also be used in sunscreen compositions.The copolymers may also be used in other compositions such as may berecognized by those skilled in the art.

2. Prior Art

UV light induced fading of fabric is a major concern to those residingin areas of high solar intensity. A fabric care agent which couldprovide protection from solar ultraviolet radiation and thereby retardthe rate of garment fading would therefore prove most useful toconsumers living in tropical and sub-tropical climates.

To the applicants, knowledge, the use of an otherwise water-insoluble UVabsorbing monomer in combination with a hydrophilic monomer (which bothdelivers the copolymer into an aqueous system and also providessoil-release effect) is unknown.

More particularly, it is known, for example, that poly(ethyleheterephthalate/poly(ethylene glycol) copolymers absorb onto hydrophobicsurfaces to confer soil release properties (U.S. Pat. No. 4,702,857 toProcter & Gamble; U.S. Pat. No. 4,569,772 to Colgate Palmolive, and U.S.Pat. No. 3,959,230 to Procter & Gamble). These materials are believed tofunction by hydrophilicly modifying a hydrophobic surface such as oilysoil on fabric or polyester fabric itself, deterring deposition ofhydrophobic soils including body sebum. The poly(ethylene terephthalate)unit is believed to seek and adhere to the hydrophobic surface; thepoly(ethylene glycol) portion is felt to give hydrophilic character tothe fabric surface as well as aid the polymer in transfer through theaqueous medium.

In addition, it is also well known that UV-absorbing agents such asp-aminobenzoic acid (PABA) and its derivatives have been used for nearlyhalf a century as UV screening agents (N. A. Shaath in "Sunscreens:Development, Evaluation, and Regulatory Aspects," N. J. Lowe and N. A.Shaath, Eds., Marcel Dekker, Inc., New York, 1990).

UV sunscreen agents such as PABA, however, are generally water-insolubleand there appears to be no teaching of combining such agents in carrierssuch that they may be used, for example, in fabric cleaningcompositions.

U.S. Pat. No. 4,153,744 to K. H. Remley teaches the use of atetrakis(hydroxymethyl)phosphonium salt to impart resistance to UVlight-induced shade change to vat-dyed cellulosic textile materials.These compounds are unrelated to the copolymers of the invention.Further the process for delivering the compound is time-consuming andrequires ammoniation of fabric followed by treatment with glacial aceticacid/hydrogen peroxide.

U.S. Pat. No. 4,788,054 to R. J. Bernhardt, et al. teaches the use ofN-phenylphthalisomides as ultraviolet radiation absorbers for cotton,wool, polyester, and rayon fabric. Again, these compounds are unrelatedto the copolymers of the invention. Further, an aqueous sulfuric acidvehicle is required for deposition.

In P. C. Crews et al., Text. Chem. Color, 19 (11): 21 (1987), the use of2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-octyloxybenzophenone,and 2-hydroxy-4-methoxybenzophenone as UV absorbers for museum textilesis taught. These compounds differ from those of the invention. Here,potentially carcinogenic perchloroethylene is required as the vehicle.Water-soluble 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid was alsoshown to reduce dye fading of museum textiles, but with significantyellowing of fabric.

B. Milligan et al., Polym. Degrad. Stab., 10(4):335(1985), teach the useof 2,2'-dihydroxy-4-4'-bissulphobutyloxybenzophenone as a water-solubleultraviolet light absorber for retarding the photo degradation of wool,but its synthesis requires the use of butanesultone, a suspectedcarcinogen.

None of the above-identified references make mention of soil releasepotential or teach materials that can be delivered in home laundry care.

U.S. Pat. Nos. 3,888,965, to S. L. Kwolek; 3,699,085 to T. A. Johnson;and 3,600,350 to S. L. Kwolek teach the synthesis of poly (ρ-benzamide)via homopolymerization of 4-aminobenzoylchloride hydrochloride, andGerman Patents Ger. Offen. 2,351,892 and 2,538,143 teach the synthesisof poly (ρ-benzamide) via homopolymerization of 4-aminobenzoic acid inthe presence of phosphates. In each of these references, the resultingpoly PABA is insoluble in water, dilute acid, dilute base, and mostorganic solvents, rendering its application as a UV-absorbing polymerfor fabric or skin care useless.

Japanese Patent Jpn. Kokai Tokkyo Koho 80,137,217 (Unitika Ltd.) teachesthe synthesis of poly(ethylene terephthalate)/poly(ρ-benzamide)copolymers for high modulus automobile tire cords. I. F. Osipenko, etal., Vesti Akad. Navuk BSSR, Ser. Khim, Navuk; 1:105 (1980), teach thesynthesis of poly(ethylene terephthalate)/poly(ρ-benzamide) copolymersand that the incorporation of ρ-aminobenzoic acid into poly(ethyleneterephthalate) improves fiber-forming properties and dye ability.Neither of these patents or publications mention the use of thepoly(ρ-benzamide)-based materials as UV-absorbing agents or soil-releaseagents, nor do these disclosures mention that thepoly(ρ-benzamide)-based materials are water-soluble or waterdispersible.

In each of the above-identified references, the compound used differsfrom the copolymer of the invention, there is no teaching that aUV-absorbing monomer can be delivered in an aqueous (e.g., fabric care)system, and there is no teaching or suggestion that the UV-absorbingmonomer can be used in a copolymer which imparts fade-resistance orsoil-release properties.

As such, there is a need in the art for novel copolymers comprising aUV-absorbing monomer copolymerized with a hydrophilic monomer whichallows the UV-absorbing polymer to be delivered in an aqueous system andsimultaneously provides soil release benefits.

SUMMARY OF THE INVENTION

The subject invention provides novel water dispersible or water-solublecopolymers which contain at least one UV-absorbing monomer and onehydrophilic monomer component.

These novel copolymers may be used in fabric care compositions.

DETAILED DESCRIPTION OF THE INVENTION

This invention relates to novel water-dispersible or water-solublecopolymers which contain at least one UV absorbing monomer and onehydrophilic monomer. The copolymer may optionally contain a hydrophobicmonomer component to control delivery and deposition.

More specifically, the copolymers of the invention are intended toachieve a balance in water-solubility such that they are soluble enoughto be able to deliver a normally insoluble UV monomer to a fabricsurface but sufficiently insoluble such that the monomer can stick oradsorb onto the fabric surface. To ensure that the copolymer is not sowater-soluble that it cannot adsorb onto the fabric surface, ahydrophobic comonomer may be used.

The novel copolymers of the invention may be used in fabric carecompositions.

COMPOSITIONS Surface Active Agents

The fabric care compositions in which the novel copolymers of theinvention may be used may contain an alkali metal or alkanolamine soapof a C₁₀ -C₂₄ fatty acid or they may contain one or more surface activeagents selected from the group consisting of anionic, nonionic,cationic, ampholytic and zwitterionic surfactants or, finally, they maycontain mixtures of any of these.

Examples of anionic synthetic detergents are salts (including sodium,potassium, ammonium and substituted ammonium salts such as mono-, di-and triethanolamine salts) of C₉ -C₂₀ alkylbenzenesulphonates, C₈ -C₂₂primary or secondary alkanesulphonates, C₈ -C₂₄ olefinsulphonates,sulphonated polycarboxylic acids (prepared by sulphonation of thepyrolyzed product of alkaline earth metal citrates, e.g. as described inBritish Patent Specification No. 1,082,179), C₈ -C₂₂ alkylsulphates, C₈-C₂₄ alkylpolyglycol -ether -sulphates, -carboxylates and -phosphates(containing up to 10 moles of ethylene oxide); further examples aredescribed in "Surface Active Agents and Detergents" (Vol. I and II) bySchwartz, Perry and Berch.

Examples of nonionic synthetic detergents are the condensation productsof ethylene oxide, propylene oxide and/or butylene oxide with C₈ -C₁₈alkylphenols, C₈ -C₁₈ primary or secondary aliphatic alcohols, C₈ -C₁₈fatty acid amides; further examples of nonionics include tertiary amineoxides with one C₈ -C₁₈ alkyl chain and two C₁₋₃ alkyl chains. The abovereference also describes further examples of nonionics.

The average number of moles of ethylene oxide and/or propylene oxidepresent in the above nonionics varies from 1-30; mixtures of variousnonionics, including mixtures of nonionics with a lower and a higherdegree of alkoxylation, may also be used.

Further types of nonionic surfactants are those derived frometherification of an alkyl or an alkylaryl alcohol with a reducingsugar. Particularly suitable examples are the alkyl polyglycosidesdescribed in U.S. Pat. No. 4,713,447 to Letton et al. and DE 3,827,534(assigned to Henkel). A further class of nonionics particularly usefulfor drier sheets are the distributing agents such as those described inU.S. Pat. No. 4,421,792 to Rudy et al., hereby incorporated by referenceinto the subject application.

Examples of cationic surfactants include, but are not limited to thequaternary ammonium compounds such as the monoalkyltrimethyl anddialkyldimethylammonium halides or C₁ -C₃ alkyl sulfate salts (i.e.,methyl or ethyl sulfates), alkyl pyridinium salts and substitutedimmidazolinium species. Still other useful agents are the primary,secondary and tertiary amines and the condensation products of fattyacids with an alkyl polyamine (e.g., bis(amidoamine).

Another class of cationics which are contemplated for use in thecompositions of the invention are ester linked quaternary ammmoniummaterials of the following formula: ##STR1## wherein each R₁ group isindependently selected from C₁₋₄ alkyl, alkenyl or hydroxyalkyl groups;each R₂ group is dependently selected from C12-24 alkyl or alkenylgroups; ##STR2##

n is an integer from 0-5.

These ester-linked quaternary ammonium materials are particularlypreferred for use in fabric conditioners because they are morebiodegradable than conventional quaternary ammonium materials.

Examples of amphoteric or zwitterionic detergents are N-alkylaminoacids, sulphobetaines, and condensation products of fatty acids withprotein hydrolysates although, owing to their relatively high costs,they are usually used in combination with an anionic or a nonionicdetergent.

Mixtures of the various types of active detergents may also be used, andpreference is given to mixtures of an anionic and a nonionic detergentactive. Soaps (in the form of their sodium, potassium and substitutedammonium salts) of fatty acids may also be used, preferably inconjunction with an anionic and/or a nonionic synthetic detergent.

The fabric care compositions which contain copolymers comprising UVabsorbing monomers may be heavy duty detergent compositions, powdereddetergent compositions, fabric softener compositions or fabric dryersheet compositions.

In one embodiment of the invention, the composition is a heavy dutyliquid detergent composition comprising one 1-75% by weight of adetergent-active compound, wherein the detergent active compoundincludes 0 to 40% of an anionic surfactant selected from the groupconsisting of alkyl benzene sulfonates, alkyl sulfates, and alkyl ethoxysulfates in combination with 0 to 40% of a nonionic surfactant selectedfrom the group consisting of alcohol alkoxylates, alkyl phenolalkoxylates, alkyl polyglucosides, and alkyl glycerol ethers; and

from 0 to 30% of a detergent builder selected from the group consistingof alkali metal salts of citric acid, copolymers of acrylic and maleicacid, oxydisuccinate, tartrate monosuccinate/tartrate disuccinate, C₈ toC₁₈ carboxylic acids, zeolites, condensed pohosphates, and combinationsthereof.

In a preferred embodiment, the liquid detergent composition comprises,in addition to the copolymer of the invention, the following:

    ______________________________________                                        C.sub.11.5 (Average Alkyl Benzene Sulfonate)                                                         25 to 30%                                              C.sub.12 -C.sub.15 Alcohol Ethoxylate (9 E.O.)                                                       10 to 14%                                              Sodium Citrate 2H.sub.2 O                                                                             6 to 15%                                              Sodium Borate 10H.sub.2 O                                                                            3 to 8%                                                Glycerol               3 to 8%                                                Proteolytic Enzyme     0.1 to 2%                                              Detergent Adjuncts     0.1 to 10%                                             Water                  balance to 100%                                        ______________________________________                                    

In a second embodiment of the invention, the composition is a powdereddetergent composition comprising: a) from 0 to about 40% anionicsurfactant selected from the group consisting of alkali metal orammonium salts of alkyl benzene sulfonates, alkyl sulfates, alkyl ethersulfates; b) from 0 to about 40% of a nonionic surfactant selected fromthe group consisting of alkyl alkoxylates, alkylphenol alkoxylates,alkyl polyglucosides, and alkyl glycerol ethers; c) from 5 to about 70%of a detergent builder selected from the group consisting of sodiumtripolyphosphate, sodium aluminosilicates, sodium C₈ -C₁₈ alkylcarboxylates, poly(acrylic) acid and copolymers of acrylic and maleicacid, alkyl ether carboxylates, citric acid and combinations thereof; d)from 2 to about 40% of an alkalinity buffer selected from the groupconsisting of sodium silicate, sodium carbonate, and organic amines; ande) from 0 to about 40% sodium sulfate.

In a third embodiment of the invention the composition is a fabricsoftener composition comprising from 2 to about 40% of a mixturecomprising: a) from 0 to about 95% of a cationic ammonium salt selectedfrom the group consisting of alkyl or alkaryl quaternary ammonium salts,alkylpyridinium salts, and substituted imidazolinium salts; b) from 0 toabout 95% of primary, secondary or tertiary amines; c) from 0 to about95% of the condensation product of a C₈ to C₁₈ alkyl carboxylic acid andan alkylpolyamine; and d) from 0 to about 40% of a polysiloxane oralkyl, alkoxy, or alkylamine modified polysiloxane.

In a fourth embodiment of the invention, the composition is a fabricdryer sheet comprising: a) from 5 to 40% of a fabric softening orantistatic agent selected from the group consisting of cationic alkyl oralkaryl ammonium salts, alkyl pyridinium salts, alkyl amines, clays andpoly siloxanes; b) from 2 to about 90% of a dispersing agent selectedfrom group consisting of urea, ammonium carboante, ethoxylated alkanols,polyethylene glycols, and block copolymers of a polyethylene glycol andpolypropylene glycol; and c) a baking strip or sheet carrying saidcomposition.

In general the surfactant used in the various fabric care compositionsof the invention will comprise from about 1-75% by weight of thecomposition, preferably from about 20-40% by weight.

The copolymer used in the compositions of the invention may comprisefrom 0.01 to 10% by weight of the composition, preferably from 0.05 to5% by weight, most preferably from 0.1-3%. It should be noted that in astandard formulation, the copolymer generally will comprise from0.01-5%, preferably 0.1-3% of the composition but that the upper rangemay increase if the copolymer is included as part of a concentratecomposition.

As will be apparent from some of the compositions already describedabove, a number of optional ingredients as are well known to thoseskilled in the art may be added to the fabric care compositions of theinvention in addition to surfactants and the copolymer containing a UVmonomer. For example, the fabric conditioning compositions may includesilicones, such as predominately linear polydialkylsiloxanes, e.g.polydimethylsiloxanes; soil release polymers such as block copolymers ofpolyethylene oxide and terephthalate; fatty amines selected from thegroup consisting of primary fatty amines, secondary fatty amines,tertiary fatty amines and mixtures thereof; amphoteric surfactants;smectite type inorganic clays; anionic soaps; zwitterionic quaternaryammonium compounds and nonionic surfactants.

The fabric conditioning compositions may also include an agent whichproduces a pearlescent appearance (e.g., an organic pearlizing compoundsuch as ethylene glycol distearate, or inorganic pearlizing pigmentssuch as microfine mica or titanium dioxide (TiO₂) coated mica. Otheroptional ingredients include emulsifiers, electrolytes (for example,sodium chloride or calcium chloride) preferably in the range from 5 to500 ppm, optical brighteners or fluoroescent agents preferably in therange from 0.01 to 5% by weight, buffers, perfumes preferably from 0.1to 5% by weight, germicides, bactericides, and bacteriostatic agents.Bacteriostatic agents are preferably employed in the range from 1 to1000 ppm, based on % active of such agent.

Similarly, if the composition is a heavy duty detergent, thecompositions may include water soluble and/or water insoluble detergentbuilder salts, alkalinity buffers (e.g., monoethanolamine,triethanolamine, borax and the like), hydrotropes (e.g., ethanol, sodiumxylene sulfonate, sodium cumene sulfonate and the like), clays,antisettling agents (e.g., aluminum stearate), soil-suspending oranti-redeposition agents, optical brighteners, anti-foam agents andbactericides.

The list of optional ingredients is not intended to be exhaustive andother optional ingredients which may not be listed but one well known inthe art may be included in the various compositions.

Copolymers

The copolymers of the invention may be defined by the following formulaI:

    --(A).sub.n --(B).sub.m --(C).sub.p --                     (I)

wherein A is a monomer capable of absorbing ultraviolet radiation in the280-400 nanometer (nm) range and bearing the appropriate bifunctionalityfor incorporation into the main chains of the polymer. Examples of suchgroups include planar aromatic based moieties such as aminobenzoateesters, anthranilate esters, salicylate esters, hydroxycinnamate esters,hydroxycarboalkoxybenzophenones, hydroxycarboalkoxydibenzoylmethanes,carboalkoxycinnamate esters, dihydroxy- anddicarboxyalkoxybenzophenones, dihydroxy- and dicarboxy-benzoylmethanes,dihydroxy-, dicarboalkoxy-, and hydroxycarboalkoxy- substitutedbetacarotenes, and dihydroxy- dicarboalkoxy-, and hydroxycarboalkoxy-substituted vitamin E derivatives;

B is a hydrophilic monomer incorporated to confer hydrophilicity tohydrophobic surfaces;

C is a hydrophobic monomer incorporated to adjust the water solubilityor water dispersibility and binding strength to hydrophobic surfaces;

n is at least 1 and may range from 1 to 500 preferably 50-500;

m is at least 5 and may range from 5 to 500; and

p may be zero and may range from 0 to 500.

It should be noted that if A (the UV-absorbing monomer) is water soluble(in that there is no precipitation from aqueous solution at aconcentration of about 0.01 weight percent), then p (defining the chainlength of the hydrophobic monomer) should be at least 1 to ensuredeposition of the polymer. Also if the length of the hydrophilic monomer(defined as B) or the percentage of B as a total percentage of thecopolymer is such that the resulting copolymer is too water soluble toeffectively absorb onto hydrophobic surfaces, then p must be greaterthan 0 and large enough to ensure that adsorption takes place while atthe same time not so large as to preclude water dispersibility.

In general, the level of m is chosen to balance the waterdispersibility, substantially and hydrophilic character of the depositedcoating. In practice, a minimum value for m of approximately 5 isuseful.

The monomer A may comprise 1 to 99.9 mol % of the polymer, preferably5-75%, most preferably 20-70 mol %, the hydrophilic monomer B maycomprise 0.05 to 49.9 mol % of the polymer, preferably 10 to 45%, mostpreferably 20-40 mol % and the hydrophobic monomer C, if present, maycomprise 0.05 to 49.9 mol % of the polymer, preferably 10 to 45%, mostpreferably 20-40%.

Although A, B, and C are expressed above as a copolymer, it is to beunderstood that the places of A, B and C may be interchanged.

The block copolymers of the invention may be further defined by thefollowing formula II: ##STR3## wherein:

R is a difunctional aryl or alkyl group such as, for example,difunctional benzene or napthalene, preferably difunctional benzene or adifunctional straight or branched alkyl chain containing 4 to 16 carbonatoms;

R₁ is hdyrogen or an aliphatic containing group having 1-20 carbons,preferably a straight-chained alkyl group having 1-12 carbons, mostpreferably 1 to 5 carbons, an aryl, an alkaryl, a secondary amine suchas, for example, dialkylamine, an alkali metal sulfonate, an alkalimetal carboxylate, an alkyl ether or a halogen atom;

R₂ is a straight or branched chain alkoxy group having 1 to 16 carbons,preferably 1 to 4 carbons, or an aryloxy or a substituted aryloxy group;

R₃ is a straight or branch chain alkyl group having 1 to 16 carbons,preferably a 1-3 carbons; and

R₄ is a UV absorbing-monomer bearing the appropriate bifunctionality forincorporation into the main chain of the polymer. By bifunctional ismeant any UV absorbing monomer as defined above bearing at least thefunctional groups such as are well known to those skilled in the art.Examples include amines, esters, carboxylic acid, hydroxyl groups etc.

x, which represents the number of monomeric units of the optionalhydrophobic group, is selected such that the hydrophobe is present at0-49.9 mol % of the polymer;

y is selected such that the R₂ group is present at 0-49.9 mol % of thepolymer;

z is selected such that the (OR₃)_(n) group is present at 0-49.9 of thepolymer wherein n is an integer between 2 and 200, preferably 10 to 25;and

w is selected such that the R₄ is present at 0.05-99.9 mol % of thepolymer.

It should be noted that w & z must equal at least 0.05 mol %.

As discussed above, the UV absorbing monomer (represented above by R₄)is a moiety bearing the appropriate bifunctionality for incorporationinto the main chain of the polymer. The UV-absorbing monomer shouldabsorb in the UVB (280-320 nm) and/or the UVA range (320-400 nm).Preferred monomers are either highly conjugated and/or poly(ene) basedderivatives and/or aromatic-based derivatives bearing the appropriatedifunctional group. Examples of such UVB and/or UVA absorbers which maybe used include p-aminobenzoate esters, m-aminobenzoate esters,anthranilate esters, salicylate esters, 2, 3, and 4-hydroxycinnamateesters; 2,2', 3,3', and 4,4'-dihydroxy and dicarboalkoxy benzophenonesand isomeric mixtures thereof; 2,2', 3,3', and 4,4'-dihydroxy anddicarboalkoxydibenzoylmethanes and isomeric mixtures thereof; and2,2',3,3', and 4,4'-dihydroxy- and dicarboalkoxydibenzalacetones.Particularly preferred is methyl 4-aminobenzoate because of its ease ofpreparation and commercial availability. Still other examples of UVabsorbing monomers which can suitably be used by those skilled in theart may be found in Shaath, N. A., Encyclopedia of UV absorbers forSunscreen Products. Cosmetics and Toiletries, 1987, March (pp 21-39).

As discussed above, the UV absorbing monomer may be added as 0.05-99.9mol % of the polymer, preferably 5-75% mol %, most preferably 20-70%.

The hydrophilic component (represented by R₂ and (OR₃)_(n)) isincorporated to confer hydrophilicity to naturally hydrophobic surfacessuch as soiled cotton or polyester as well as to facilitate transfer ofthe polymer through an aqueous medium. Hydrophilic monomers which may beused include, but are not limited to the α,ω-diols or alkylene glycolssuch as ethylene glycol, propylene glycol, butylene glycol, and mixturesof the three. Other hydrophilic monomers which may be used as R₂ arebased on simple sugars or poly(saccharides), or α,ω-poly(ols) which mayinclude glucose, sucrose, sorbitol or glycerol.

In a preferred embodiment of the invention, R₂ is an ethylene glycol and(OR₃)_(n) is a poly(ethylene glycol). Suitable polyethylene glycols arethose manufactured by Union Carbide and sold under the CARBOWAX®tradename. Examples include CARBOWAX® 300, 600, 1000, 3350 and the like.It is not absolutely required that the ethylene glycol monomeric unit bepresent as part of the final copolymer although generally the moleculeis present as 5-30 mol %, preferably 10-30% mol % of the polymer.

The poly(ethylene glycol), however, must be present in at leastsufficient quantity to ensure that the final copolymer may be deliveredthrough an aqueous medium. In general, this monomer is present as 5-45mol %, preferably 20-45% of the polymer.

In general, applicants have found that the reaction works favorably whenthe poly(ethylene glycol) is mixed with the ethylene glycol in a molarratio of about 1.5:1. There is no criticality to this ratio, however,and the copolymer will form within any of the broad ranges describedabove.

The hydrophobic monomer which may be optionally incorporated is used toadjust the water solubility and binding strength of the copolymer tohydrophobic surfaces. As noted above, this monomer should be present ifthe UV absorbing monomer is water-soluble or if the percentage of y & zis so high that the polymer is too water soluble to adsorb ontohydrophobic surfaces. Suitable hydrophobic monomers which may be usedinclude long chain aliphatic α,ω-diols, α,ω-diamines, orα,ω-dicarboxylates. Another suitable class of hydrophobic monomersincludes the aromatic 4,4'-phenylenediols, 4,4'-biphenols, or4,4'-dihydroxydiphenyl ethers, as well as the analogous dicarboxy ordiamino species. Especially preferred monomers are terephthalic acid andhexanedioic acid.

These monomers are generally added as 0.05-49.9 mol % of the reactionmixture, preferably 10-45 mol %.

In one especially preferred embodiment of the invention, the UVabsorbing monomer is methyl 4-aminobenzoate, the hydrophilic monomer isa mixture of poly(ethylene glycol) and ethylene glycol and thehydrophobic monomer is dimethyl terephthalic acid.

The molecular weight of the copolymers may range from oligomers of about750 to polymers of 100,000, preferably 1,000 to 15,000, and mostpreferably 2,000 to about 10,000. The ratio of monomers can vary broadlydepending upon the end use requirements such as whether the polymer isbeing used for soil release, antiredeposition, or enzyme stabilization.

However, as is usual for soil release agents, some balance is generallysought between hydrophilic and hydrophobic properties. These can be finetuned by those skilled in the art.

As mentioned above, in one embodiment of the invention, the copolymersof the present invention may be based upon the condensation product ofdimethyl terephthalate, ethylene glycol, poly(ethylene glycol), andmethyl 4-aminobenzoate.

The polyethylene glycol used will generally have a molecular weightranging from about 200 to about 10,000.

These components may be combined via a 1-step transesterificationreaction as set forth below: ##STR4##

According to the above scheme, the hydrophobic poly(ethyleneterephthalate) unit has been incorporated to adhere the polymer tohydrophobic surfaces such as oily soil residue on cotton fabric orpolyester-based fabric. The hydrophilic poly(ethylene glycol) unit hasbeen incorporated to facilitate polymer transfer through an aqueousmedium and to modify a hydrophobic surface to a more hydrophilic state,thereby deterring oily soil build-up. The methyl 4-aminobenzoate unithas been incorporated primarily to provide anti-fading benefits. Themethyl 4-aminobenzoate was obtained commercially.

Polymers were obtained by charging the reaction vessel with 1 eq ofdimethyl terephthalate, 2 eq. of the ethylene glycol-poly(ethyleneglycol) mixture, 0.5-3 eq. of 4-aminobenzoate, and suitable catalystssuch as Ca(OAc)₂. The contents of the reaction vessel were heatedbetween 175°-220° C. for between 26-30 hours. The resulting materialsranged in molecular weight from 1,000-15,000 and absorbed UV light inthe UVB (280-320 nm) range.

The following examples are intended to further illustrate the inventionand are not intended to be limiting in any way.

EXAMPLE 1 General Procedure for Preparation of Polymers

To a 250 mL 3-neck round bottom flask fitted with an overhead stirrer,distillation condensor, and nitrogen inlet tube was added 5.59 g (28.8mmol) dimethyl terephthalate, 2.15 g (34.7 mmol) ethylene glycol, 33.45g (23.1 mmol) poly(ethylene glycol) MW=1450, 6.05 g (40.0 mmol) methylρ-aminobenzoate, 0.031 g (0.20 mmol) Ca(OAc)₂, 0.031 g (0.11 mmol) Sb₂O₃, and 0.031 g (0.14 mmol) 2,6-di-tert-butyl-4-methylphenol. Thereaction vessel was purged with nitrogen and wa heated at 175° C. for 2h. The temperature was raised to 205° C., at which point MeOH began todistill off, and was heated at that temperature for 5 h. The temperaturewas further raised to 220° C. and heated at that temperature for anadditional 19 h. The reaction mixture was allowed to cool to roomtemperature, where upon the polymer was removed. Optionally, thereaction mixture was allowed to cool 80° C., and was placed under vacuum(2 torr). The reaction mixture was reheated to 220° C., and was kept atthat temperature for 4 h. The vacuum was removed and the reactionmixture was allowed to cool to room temperature under nitrogen.

¹ H NMR (CDCl₃, 200 MHz), δ 3.68 (broad s, (--CH₂ CH₂ O)_(x-)), 3.84 (t,J=4.7 Hz, --HNC₆ H₄ CO₂ CH₂ CH₂ O--(CH₂ CH₂ O)_(x-)), 3.84 (t, J=4.7 Hz,--OCC₆ H₄ CO₂ CH₂ CH₂ O--(CH₂ CH₂ O)_(x-)), 4.40 (t, J=4.7 Hz,

--HNC₆ H₄ CO₂ CH₂ CH₂ O--(CH₂ CH₂ O)_(x-)), 4.49 (t, J=4.7 Hz, --OCC₆ H₄CO₂ CH₂ CH₂ O--(CH₂ CH₂ O)_(x-)), 4.63 (s, --HNC₆ H₄ CO₂ CH₂ CH₂ O₂ CC₆H₄ NH--), 4.7(s, --OCC₆ H₄ CO₂ CH₂ CH₂ O₂ CC₆ H₄ CO--), 6.64 (d, J=8.0Hz, --HNC₆ H₄ CO--), 7.85 (d, J=8.0 Hz, --HNC₆ H₄ CO--), 8.11 (s, --OCC₆H₄ CO--).

EXAMPLE 2 Preparation and Characterization of Polymers by GPC and UVSpectrochotometry

A series of poly(ethylene terephthalate)/poly(oxyethyleneterephthalate)/poly(ρ-benzamide) polyamide/esters were synthesizedaccording to the procedure described in Example 1. Samples werecharacterized by UV spectroscopy and gel permeation chromatography(GPC), using chloroform as the solvent. Molar extinction (ε) wascalculated based upon the Beer's Law equation ε=A/cl, where A=absorbanceas measured by the UV spectrometer, 1=path length, and c=the molarconcentration. In the case of these polymers, molarity was based uponthe molecular weight of the average repeating unit. The results arepresented below in Table 1:

                  TABLE 1                                                         ______________________________________                                                                       PABA    ε                              Polymer                                                                              MW      λ max                                                                          PEG MW  (mol. eq.)                                                                            (l/mol-cm)                             ______________________________________                                        A      1,000   284 nm    600   0.60    4,900                                  B*     4,800   286 nm    600   0.20    4,600                                  C*     2,700   286 nm    600   0.50    7,900                                  D      2,600   286 nm    600   0.50    7,000                                  E      2,000   286 nm    600   0.60    8,400                                  F*     11,300  286 nm  1,450   0.20    3,400                                  G*     9,000   285 nm  1,450   0.33    7,500                                  H      6,700   283 nm  1,450   0.50    8,800                                  I*     6,800   284 nm  1,450   0.50    6,500                                  J*     9,100   286 nm  1,450   0.50    6,000                                  K      5,800   284 nm  1,450   0.60    8,900                                  L*     5,600   284 nm  1,450   0.60    8,900                                  M      11,700  281 nm  3,350   0.50    8,900                                  N      11,100  283 nm  3,350   0.60    10,700                                 O      1,700   283 nm    600   0.50    5,300                                  P      13,700  280 nm  3,400   0.50    7,770                                  ______________________________________                                         *Vacuum employed                                                              MW = molecular weight as determined by gel permeation chromotography (GPC     λ max = wavelength (nanometers) of maximum absorbance                  PEG MW = poly(ethylene glycol) molecular weight as specified by supplier      PABA = methyl 4aminobenzoate                                                  ε = extinction (i.e. A/cl) as defined by Beer's Law              

EXAMPLE 3 Anti-Fading Evaluation: Polymer Delivery Via ChloroformVehicle Onto Green Cotton

Solutions of anti-fade polymers of the present invention were preparedby dissolving 2 g of anti-fade polymer in 50 g of chloroform. Solutionswere sprayed from a Humbrol Spray Gun onto 10×15 cm swatches of greencotton. Approximately 0.04 g of the anti-fade polymers were depositedonto each test cloth. The test swatches were exposed to simulated solarradiation via an Atlas Ci65a Weather-O-meter for 45 h. The spectraloutput (xenon arc radiation filtered through borosilicate glass)approximates Miami (25°46' north latitude) daylight. Test conditionsmeet BS 1006 and DIN standards for light fastness testing. Anti-fadeprotection was assessed by reflectance spectroscopy using an ICSMicromatch Reflectance Spectrophotometer. The percent anti-fadeprotection was calculated as the change in reflectance (Ks) from theuntreated to the treated cloths, relative to the untreated cloths, i.e.,

% Anti-fade protection=(Ks untreated-Ks treated)+Ks untreated

The results for green cotton are shown below in Table 2:

                  TABLE 2                                                         ______________________________________                                                                    PABA    % Anti-Fade                               Polymer MW       PEG MW     (mol. eq.)                                                                            Protection                                ______________________________________                                        D       2,600    600        0.50    24.8                                      E       2,000    600        0.60    30.0                                      H       6,700    1,450      0.50    18.6                                      P       13,700   3,400      0.50     2.6                                      K       5,800    1,450      0.60    11.2                                      A       1,000    600        0.60    18.1                                      O       1,700    600        0.50    16.8                                      C       2,700    600        0.50    30.1                                      ______________________________________                                    

This Example shows that, of the polymers from Table 1 tested, anti-fadeprotection ranging from 2.6-30% increases were found. The Example showsthat a UV absorbing monomer can be incorporated into a water dispersibleor water soluble copolymer which can be used in a solvent vehicle andthat the copolymer will provide anti-fading effect.

The polymers cause no noticeable staining of the fabric.

It should be noted that not all polymers of Table 1 were tested but thatthe polymers of Table 2 were selected as representative examples havingan adequate distribution of molecular weight and PABA loading.

EXAMPLE 4 Anti-Fading Evaluation: Polymer Delivery Via ChloroformVehicle Onto Blue Polyester

Solutions of anti-fade polymers of the present invention were preparedby dissolving 2 g of anti-fade polymer in 50 g of chloroform. Solutionswere sprayed from a Humbrol Spray Gun onto 10×15 cm swatches of bluepolyester. Approximately 0.04 g of the anti-fade polymers were depositedonto each test cloth. The test swatches were exposed to simulated solarradiation via an Atlas Ci65a Weather-0-Meter for 45 h. The spectraloutput (xenon arc radiation filtered through borosilicate glass)approximates Miami (25°46' north latitude) daylight. Test conditionsmeet BS 1006 and DIN standards for light fastness testing. Anti-fadeprotection was assessed by reflectance spectroscopy using an ICSMicromatch Reflectance Spectrophotometer. The percent anti-fadeprotection was calculated as the change in reflectance (Ks) from theuntreated to the treated cloths, relative to the untreated cloths, i.e.,

% Anti-fade protection-Ks untreated-Ks treated)+Ks untreated

The results for blue polyester are shown below in Table 3:

                  TABLE 3                                                         ______________________________________                                                                    PABA    % Anti-Fade                               Polymer MW       PEG MW     (mol. eq.)                                                                            Protection                                ______________________________________                                        H       6,700    1,450      0.50    3.6                                       A       1,000    600        0.60    3.2                                       O       1,700    600        0.60    2.1                                       C       2,700    600        0.50    8.3                                       ______________________________________                                    

This example again shows that a UV absorbing monomer can be incorporatedinto a solvent vehicle and impart anti-fading effect. The selection ofpolymers in Table 3 was made on the basis of effectiveness from theresults of Table 2.

EXAMPLE 5 Anti-Fading Evaluation: Polymer Delivery Via a RinseConditioner Formulation onto Blue Polyester

Rinse conditioners containing 5% w/w Arquad 2HT (dihardened tallowdimethylammonium chloride) softener and 2.5% w/w anti-fade polymer wereprepared by adding a neat mixture of the melted solids to 70° C. waterwith vigorous agitation. These fabric care formulations were used at aconcentration of 4 g/L on 10 g swatches of blue polyester. The rinsetreatment was carried out in a terg-o-tometer at 60 rpm with 21° C.demineralized water for 5 min. The polyester fabric pieces were spun andline dried. These test swatches were exposed to simulated solarradiation via an Atlas Ci65a Weather-O-Meter for 45 h. The spectraloutput (xenon arc radiation filtered through borosilicate glass)approximates Miami (25°46' north latitude) daylight. Test conditionsmeet BS 1006 and DIN standards for light fastness testing. Anti-fadeprotection was assessed by reflectance spectroscopy using an ICSMicromatch Reflectance Spectrophotometer. The percent anti-fadeprotection was calculated as the change in reflectance (Ks) from theuntreated to the treated cloths, relative to the untreated cloths, i.e.,

% Anti-fade protection=(Ks untreated-Ks treated)+Ks untreated

The results for blue polyester are shown below in Table 4:

                  TABLE 4                                                         ______________________________________                                                                    PABA    % Anti-Fade                               Polymer MW       PEG MW     (mol. eq.)                                                                            Protection                                ______________________________________                                        H       6,700    1,450      0.50    14.9                                      A       1,000    600        0.60    1.8                                       O       1,700    600        0.50    3.4                                       C       2,700    600        0.50    3.0                                       ______________________________________                                    

This Example is similar to Example 5 and demonstrates that a UVabsorbing monomer can be incorporated into a fabric care composition andcan impart anti-fading effect.

In Table 3, delivery of the polymer was via a chloroform solvent while,in this table, delivery was via a rinse conditioner in a wash.

EXAMPLE 6 Solid Release Evaluation: Polymer Delivery Via a RinseConditioner Formulation Onto Viroin (Undyed) Polyester

Rinse conditioners containing 5% w/w dihardened tallow dimethylammoniumchloride softener (Arquad 2HT) and 1% w/w anti-fade polymer wereprepared by adding a neat mixture of the melted solids to 70° C. waterwith vigorous agitation. These fabric care formulations were used at aconcentration of 2 mL/L on 3"×10" swatches of virgin polyester. Therinse treatment was carried out in a terg-o-tometer at 60 rpm with 21°C. demineralized water for 5 min. The polyester fabrics were line dried.The test cloths were stained with a 100 μL solution of 0.06% w/w sudanred in olive oil, and left to wick for four days. Baseline reflectancedata were obtained using an ICS Micromatch ReflectanceSpectrophotometer. The test cloths were rewashed in a terg-o-tometer at40° C. with 5 g/L of a commercially available laundry detergent for 15min., rinsed at 21° C. for 5 min., and line dried. Soil release benefitfrom the anti-fade polymers was assessed by redetermining reflectance.The percent detergency (i.e., soil release) was calculated as the changein reflectance (Ks) from the cloths before to the cloths afterrewashing, relative to the cloths before rewashing, i.e.,

% Detergency=(Ks before-Ks after)+Ks before

The results for virgin polyester are shown below in Table 5:

                  TABLE 5                                                         ______________________________________                                        Polymer MW       PEG MW    (mol. eq.)                                                                            % Detergency                               ______________________________________                                        D       2,600    600       0.50    81                                         E       2,000    600       0.60    74                                         H       6,700    1,450     0.50    85                                         P       13,700   3,400     0.50    36                                         K       5,800    1,450     0.60    86                                         A       1,000    600       0.60    42                                         O       1,700    600       0.50    50                                         C       2,700    600       0.50    94                                         ______________________________________                                    

This example shows that the novel copolymer of the invention can be usednot only to impart anti-fading effect, but that it simultaneouslyimparts soil-release effect when the copolymer is incorporated in afabric composition.

EXAMPLES 7-11

Use of copolymers of the Invention in Heavy Duty Liquid (HDL)Compositions.

    ______________________________________                                                     wt. %                                                            Ingredient     7       8      9     10   11                                   ______________________________________                                        Sodium C11-C15 Alkyl                                                                         10.0    17.0   26.0  15.0 11.6                                 Benzene Sulfonate                                                             Sodium Alkyl Ethoxy                                                                          6.0     --     --    --   8.2                                  Sulfate (2)                                                                   Alcohol Ethoxylate (1)                                                                       8.0     7.0    12.0  5.0  4.2                                  Sodium Citrate 7.0     7.0    10.0  --   5.0                                  Sodium Salt of C12-C18                                                                       --      --     --    --   3.6                                  Fatty Acid                                                                    Sodium tartrate mono                                                                         --      --     --    --   3.1                                  and disuccinate                                                               Monoethanolamine                                                                             2.0     2.0    2.0   --   --                                   Triethanolamine                                                                              2.0     2.0    2.0   --   --                                   Sodium Silicate                                                                              --      --     --    2.5  --                                   Savinase       0.75    --     0.75  --   0.4                                  Sodium Borate  3.5     --     3.5   --   --                                   Sodium Formate --      --     --    --   1.2                                  Glycerol       --      --     5.0   --   --                                   Propylene Glycol                                                                             4.0     --     --    --   4.5                                  Sodium Xylene Sulfonate                                                                      3.0     3.0    --    1.0  2.3                                  Ethanol        --      --     --    --   1.0                                  Tinopal UNPA   0.25    0.25   0.2   0.1  0.2                                  FW Polyester   0.05 to 5.0                                                    Water          to 100.0                                                       ______________________________________                                         (1) C12 to C15 alcohol condensed with 9 mole ethylene oxide                   (2) C12 to C15 alcohol condensed with 3 mole ethylene oxide and sulfated 

EXAMPLES 12-16

Use of copolymers of the Invention in Powdered Detergent Compositions.

    ______________________________________                                                     wt. %                                                            Ingredient     12      13     14    15   16                                   ______________________________________                                        Sodium C11-C12 Alkyl                                                                         11.0    11.5   17.0  11.0 15.0                                 Benzene Sulfonate                                                             Sodium C12-C15 Alkyl                                                                         --      5.5    --    --   --                                   Ethoxy Sulfate (2)                                                            Sodium C12-C15 Alkyl                                                                         10.0    --     --    9.0  5.0                                  Sulfate                                                                       Alcohol Ethoxylate (1)                                                                       --      3.0    --    2.0  3.0                                  Sodium Salt of C12-C18                                                                       1.0     --     --    --   1.0                                  Fatty Acid                                                                    Sodium Tripolyphosphate                                                                      --      --     --    --   25.0                                 Sodium Aluminosilicate                                                                       25.0    15.0   20.0  10.0 --                                   Sodium Silicate                                                                              3.0     20.0   5.0   15.0 15.0                                 Sodium Carbonate                                                                             18.0    18.0   15.0  30.0 20.0                                 Savinase       0.5     0.5    0.5   0.5  1.0                                  Tinopal AMS    0.15    0.2    0.25  0.15 0.15                                 FW Polyester   0.05 to 5.0                                                    Sodium Sulfate to 100.0                                                       ______________________________________                                         (1) & (2) same as HDL compositions                                       

EXAMPLES 17-19

Use of copolymers of the invention in Fabric Softener Compositions.

    ______________________________________                                                           wt. %                                                      Ingredient           17      18      19                                       ______________________________________                                        Dimethyldialkyl ammonium chloride                                                                  3.2     6.5     6.25                                     Trimethylalkyl ammonium chloride                                                                   0.6     0.9     --                                       Alkyl amidoethyl alkyl imidazoline                                                                 3.3     16.0    --                                       Polydimethyl siloxane                                                                              0.1     0.5     --                                       Ethanol              0.7     1.4     --                                       Calcium chloride     0.1     0.3     0.1                                      FW Polyester         0.05 to 5.0                                              Water                to 100.0                                                 ______________________________________                                    

We claim:
 1. A water-soluble or water-dispersible copolymer containing aUV-absorbing monomer (absorbing in the 280-400 nanometer range) ahydrophilic group.
 2. A copolymer according to claim 1 wherein thecopolymer is a block copolymer having the formula:

    --(A).sub.n --(B).sub.m --(C).sub.p --

wherein A is a monomer capable of absorbing ultraviolet radiation in the280-400 monometer range and bears the appropriate bifunctionality forincorporation into the main claim of the polymer; B is a hydrophilicmonomer; C is a hydrophobic monomer; n ranges from 1 to 500; m rangesfrom 5 to 500; and p ranges from 0 to
 500. 3. A copolymer according toclaim 1, having the formula ##STR5## wherein: R is a difunctional arylgroup or a difunctional straight or branched alkyl chain having 4 to 16carbons;R₁ is hydrogen, an aliphatic group having 1-20 carbons, an aryl,an alkaryl, a secondary amine, an alkali metal sulfonate, an alkalimetal carboxylate, an alkyl ether or a halogen atom; R₂ is a straight orbranch chain alkoxy group having 1 to 16 carbons, an aryl or asubstituted aryl group; R₃ is a straight or branch chain alkyl grouphaving 1 to 16 carbons; R₄ is a UV-absorbing monomer absorbing in theUVB (280-320 nm) and/or UVA (320-400 nm) range; x is selected such thatthe hydrophobe is present at 0-49.9% of the polymer; y is selected suchthat the R₂ group is present at 0-49.9 mol % of the polymer; z isselected such that the (OR₃)_(n) group is present at 0 to 49.9 mol % ofthe polymer wherein n is an integer between 2 and 200; and w is selectedsuch that R₄ is present at 0.05-99.9 mol % polymer; and w & z equals atleast 0.05 mol %.
 4. A copolymer according to claim 3, wherein R is adifunctional benzene or naphthalene.
 5. A copolymer according to claim3, wherein R₁ is hydrogen or a straight chain alkyl group having 1 to 12carbon atoms.
 6. A copolymer according to claim 3, wherein R₂ is analkoxy group having 1-4 carbons.
 7. A copolymer according to claim 3wherein R is ##STR6## and R₁ is hydrogen.
 8. A copolymer according toclaim 3 wherein R₂ is --OCH₂ CH₂ --.
 9. A copolymer according to claim 3wherein R₃ is --CH₂ CH₂ --.
 10. A copolymer according to claim 3 whereinR₄ is a highly conjugated and/or poly(ene)-based derivative and/oraromatic based derivative bearing a difunctional group.
 11. A copolymeraccording to claim 3 wherein R₄ is ##STR7##
 12. A copolymer according toclaim 3 whereinR is ##STR8## and R₁ is H; R₂ =--OCH₂ CH₂ --; R₃ =--CH₂CH₂ --; and R₄ is a highly conjugated and/or poly(ene)-based derivativeand/or aromatic based derivative having a difunctional group.
 13. Acopolymer according to claim 3 whereinR is ##STR9## and R₁ is H; R₂=--OCH₂ CH₂ --; R₃ =--CH₂ CH₂ --; and R₄ = ##STR10##
 14. A copolymeraccording to claim 3 prepared by polymerizing a mixture of dimethylterephthalate, ethylene glycol, polyethylene glycol of MW 200-3000 andmethyl 4-aminobenzoate.